Layered piezoelectric structures have found wide applications in micro-electro-mechanical systems (MEMS) due to their intrinsic electro-mechanical coupling effect. The adhesion effect resulting from various surface forces (e.g., the electrostatic force, capillary force, and Van der Waals force) has become one dominant factor in determining the reliability and service life of the MEMS devices. In this study, the asymmetric non-slipping adhesion behavior of layered piezoelectric structures under the action of different external loadings is investigated. A system of coupled singular integral equations are obtained for the stated problem in the framework of the generalized JKR theory, where the coupling effect between the normal and tangential contact stresses is taken into consideration. The closed-form analytical solutions of the electric displacement and stress fields within the contact zone are derived. The relations between the contact size and applied loadings are set up with the Griffith energy balance criterion. The effect of the mechanical and electric loads and the mismatch strain on the adhesion behavior of layered piezoelectric structures is discussed in detail. It is found that applying the electric load can only strengthen the adhesion effect for different types of layered piezoelectric structures. Both the inclined angle of the mechanical force and the geometric parameter of the contacting objects have significant effects on the adhesion behavior. The results obtained from present paper should be very useful for understanding the adhesion failure mechanism of the MEMS devices composed of layered piezoelectric structures.